Natural Fiber Reinforced Geopolymer Composites

W. M. Kriven Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, IL

Supported by US Air Force Office of Scientific Research, Army Research Office, US Army Corps of Engineers and Dow Chemical Company

1 Contributors • M. Gordon • S. S. Musil • J. L. Bell • Shinhu Co • P. E . Driemeyer • K. Sankar • R. P. Haggerty • P. F. Keane • S. Mallicoat • Daniel Ribero • N. Xie • Daniel Roper • D. R. Lowry • E. Rill • Eli Koehler • P. Duxson • Dr. Ruy Sa Ribiero • J. Provis • Marilene Sa Ribiero • Un Heo • Dr. A. Bhuiya • Dr. Pankaj Sarin • Dr. Qun Yang • B. Glad • Brian Munoz

2 Keramos Mug Drop Competition - ACERS 2005

Testing for leaks ………

The 5 storey plummet ……… WATER REMOVAL

TGA Results*

Water Dryout: RT –350oC Most of water evaporated below 250oC leading to a 5% shrinkage*

This includes free water at surface/pores, adsorbed water, and chemically bound water*

*Rahier, H., B. VanMele, and J. Wastiels, Low-temperature synthesized aluminosilicate glasses: Part II: Rheological transformations during low-temperature cure and high-temperature properties of a model compound. Journal of Materials Science, 1996. 31 80-85, (1996) Dehydration Cracking • Geopolymers undergo shrinkage upon heating due to water loss1 – RT to 100oC: Dehydration of physically bonded (free) water – 100 to 300oC: Dehydration of chemically bonded (interstitial) water – >300oC: Dehydroxylation of OH groups • This is described by the Young and La Place Equation: DP = (2g cos f) / r • Dehydration shrinkage causes cracking of monolithic geopolymer • Reinforcing or filler phases can be utilized to maintain structural integrity during shrinkage by crack-bridging and offering pathways for more graceful dehydration

1J. Davidovits, Geopolymer Chemistry and Applications, 2008.

9 Reinforcements • Chamotte/mullite particulates, granite, dolomite sediment • Chopped fibers – Alumina (13 µm D x 100 µm long) – Basalt (50 µm D x ¼”, ½” long) – Carbon (7 µm D x 60 or 100 µm long) • Alumina platelets (D = 50 µm) • Woven fabric – Carbon fiber – Nextel 610 alumina, 720 mullite + alumina, 550 mullite – Basalt weaves and felts • Mullite single crystal fibers (Moscow) • Polymeric chopped fibers – polyproplyene (½”, 1”, 2”) • Biological fibers – Corn husk fiber bundles - Cordgrass (Illinois) – Jute (China, India) - Abaca (Manila hemp) and Hemp – Fique (Colombia) - Malva (Amazon) – Cork - Curaua (Amaon) BENCHMARK STRUCTURAL PROPERTIES of GP CERAMIC COMPOSITES Material Flexure strength (MPa) • KGP-chamotte particulate • 2.1 15.3 for 50 wt% • Alumina platelets • 2.0 20 (or 40 at HT) • KGP-chopped basalt ¼” f =13 µm • 1.7 19.5 for 10 wt% ½” f=13 µm • 2.2 27 for 10 wt% • Chopped C fiber 60 µm f =7 µm • 8.8 14.1 for 10 wt%

• Chopped Al2O3 fiber CsGP f = 3 µm • 10 20 for 20 wt% • Nextel 610 weave • 8.7 50 for 33 vol% • Nextel 720 weave • 8.7 40 for 27 vol % • Basalt plain weave • 4.5 41.4 for 30 vol% • Chopped strand mat • 4.5 31.7 for 20 vol % Tensile strength (MPa) • Nextel 610 weave in KGP • 2.5 205 • Nextel 720 weave in KGP • 2.5 125 • Plain basalt weave in KGP • 1.2 38 • Nextel 610/monazite in alumina • 0.25 117 Basalt chopped strand mat reinforced GP Composites

(A) (B)

(C) (D)

Synthetic and Biological Fiber Reinforcements

Material • NaGP-polypropylene • ½”, 1”, 2” • Corn husk fibers • China jute weave • Colombian fique • Brazilian malva • Brazilian curaua • Abaca (Manila hemp) SEM of Polyproplyene Fibers

Innegrity Polypropylene (PP) (a) 0.5" fibers with diameter 47±1 µm (b) 1" fibers with diameter 50±1.5 µm (c) 2" fibers with diameter 48±1 µm. Optical micrograph of PP-geopolymer composite broken in 3-point flexure (side view) Optical micrograph of PP-geopolymer composite broken in 3-point flexure (top-side, hairy view) Optical micrograph of PP-geopolymer composite broken in 3- point flexure (bottom view) 3-pt flexure of PP fiber - geopolymer composites

20

18

16

14

12

10 0.5"

1" 8 2"

6

4 Average Three Point Flexure Failure Strength (MPa)

2

0 0 0,5 1 1,5 2 2,5 3 wt% of fiber reinforcement

Average maximum failure stress of sample as a function of fiber length and composition NaGP/CHF Composite Panels • The uncured panel was then covered with a Delrin top piece and placed in a hydraulic press at 50 psi for 24 hours to compress the panel and remove excess geopolymer matrix material • Following the cold press process, the panel mold was sealed and placing in the oven at 50oC for 24 hours for final curing • Cured panels were cut into mechanical testing samples using a wet tile saw with high speed diamond abrasive cutting wheel – Flexural test specimens: 10 mm x 60 mm – Straight-sided tensile test specimens: 25 mm x 150 mm

Mf Fiber Orientation Wetted/Unwetted Panel 1 13.28% Quasi-aligned Wetted Panel 2 12.99% Quasi-aligned Unwetted Panel 3 14.45% Random Wetted Panel 4 12.01% Random Unwetted

20 In the Amazon (Manaus, Brazil)………… As-received jute reinforced sodium geopolymer plate Plate impact testing apparatus

Schematic Apparatus Plate impact testing

Figure shows 4” x 4” jute plates(left) after plate impact testing Impact tests

35

30.58 30

25

20 Malva Jute Fique 15 Curaua (maximum) Energy Absorbed (J) Energy

10 9,35 9,39

5 2.20

0 SEM of Curaua Fiber-reinforced Geopolymer Synthetic and Biological Fiber Reinforcements

Material Flexure Strength (MPa) • NaGP-polypropylene • 1.8 18.3 for 2.5 wt% (2”), • ½”, 1”, 2” 15 MPa (1”), 14.5 (½”) • Corn husk fibers • 2.5 7.6, pullout 15.3% strain • China jute weave • 2.5 20.5 treated, 15 untreated

• Colombian fique • 2.5 11.4 I-D treated 7.1 2-D treated • Brazilian malva • 2.5 18.3 • Brazilian curaua • 2.5 12.8 • Abaca (Manila hemp) • 7.9 52.3 “Abaca” fiber, also known as “Manila hemp,” is grown in the Phillippines, Ecuador and Costa Rica The extremely strong fibers are often used in twine and ropes, and can be pulped to make specialized paper Amazonian Bamboo Fast growing and high yield renewable resource Readily available in Brazil Governmental support 40-50 culms per clump 10-20 culms yearly Maximum height in 4-6 months Daily increment of 150-180mm 4 years to mature Reactivity of Amazonian Metakaolin for Geopolymer Synthesis

Mineral reserves as Brazil source of aluminosilicates

Photo by Ruy A. Sá Ribeiro Reactivity of Amazonian Metakaolin for Geopolymer Synthesis

Amazonian MK

Replacing Portland Cement

Photo by Ruy A. Sá Ribeiro Potassium-Based Geopolymer Reinforced with Bamboo Fibers

Mineral reserves and Brazil byproducts as source of aluminosilicates

Photo from brminer.com Potassium-Based Geopolymer Reinforced with Bamboo Fibers Fibers, particles and strip of native or natural materials grown in the Amazon

Promote higher strength, rigidity, and workability, generating green high- performance materials

Photo from flickr.com/lozanoginel Potassium-Based Geopolymer Reinforced with Bamboo Fibers

Regional and local materials in the production of geopolymeric composites reduce environmental impacts and raise their practicality

Photo from flickr.com/nasfizo Potassium-Based Geopolymer Reinforced with Bamboo Fibers

Bamboo fibers

Low cost High strength and biodegradability

Absorption of CO2 and production of O2 3 times more than other plants

Photo from flickr.com/harnisch Guadua Angustifolia

Strong Colombian bamboo Collaboration with INPA (Instituto National de Pesquinsas de Amazonas) Reactivity of Amazonian Metakaolin for Geopolymer Synthesis Experimental procedures

Chopped bamboo fibers micro BF1A and short BF4W fibers Experimental procedures Mixed Alkali Regional Metakaolin-Based Geopolymer 1 = powder 4 = fibers

GPC Compressive Strength ASTM C1424-10 KNa-MKA / KNa-MKA-BF1A / KNa-MKA-BF4A / KNa-MKA-BF4W Chopped Guadua Angustifolia bamboo reinforcements

Panels and test samples of 6 “ x 8 “ Experimental procedures Mixed Alkali Regional Metakaolin-Based Geopolymer

Third-Point Loading Flexural Strength ASTM C1341-13 KNa-MKA-BF1A/BF4W Using natural Amazonian clay Experimental Reactivity of Amazonian Metakaolin for Geopolymer Synthesis procedures

GPCs’ strengths tested in compression and flexural loading Reactivity of Amazonian Metakaolin for Geopolymer Synthesis KNa-MKA76

KNa-MKA67 Na-MKA76 XRD and SEM techniques used to characterize the material Reactivity of Amazonian Metakaolin

100,00 for Geopolymer Synthesis

90,00 83,37

80,00 70,25 70,00 57,81 60,00

50,00

40,00

30,00 Compressive Strength (MPa) 20,00

10,00

0,00 KNa-MKA67-5x12 KNa-MKM-5x12 Na-MKA76-5x12 K-MKM-5x12 12 GP 10.95 10.49

10 ) a

P 7.95

M 8 7.50 (

Test results demonstrate h t g n e

r 6 the great effect of highly t S

l a r u

x 4 e reactive MKA on GP l F strength 2

0 KNa-MKA76-BF4W Na-MKA76 KNa-MKA76-BF1A K-MKM GPC SEM KNa-MKA GP KNa-MKA-BF4W GPC

Scale σ σ SD L95% U95% GPC o c-avg Modulus β (MPa) (MPa) (MPa) (MPa) (MPa) Shape

KNa-MKA76 11.590 58.20 55.70 5.83 51.98 60.12

KNa-MKA76-BF1A 3.303 33.11 29.70 9.90 22.91 38.08

KNa-MKA76-BF4A 15.38 24.76 23.93 1.91 22.75 25.24

KNa-MKA76-BF4W 12.010 28.07 26.90 2.72 25.37 28.84

70,00 60,00 55,70 Compressive Strength 50,00

40,00 29,70 26,90 30,00 23,93

20,00

Compressive Strength (MPa) 10,00

0,00 KNa-MKA76 KNa-MKA76-BF1A KNa-MKA76-BF4A KNa-MKA76-BF4W GPC Flexure Strength

Scale σ σ SD L95% U95% GPC o f-avg (MPa) (MPa) (MPa) (MPa) (MPa) Modulus β Shape

KNa-MKA76-BF1A 1.323 6.59 6.07 4.63 3.96 7.73

KNa-MKA76-BF4W 8.619 7.50 7.09 0.98 6.52 7.71

8,00 7,09 7,00 6,07 6,00

5,00

4,00

3,00

Flexural Strength (MPa) 2,00

1,00

0,00 GPC KNa-MKA76-BF1A KNa-MKA76-BF4W Reactivity of Amazonian Metakaolin for Geopolymer Synthesis Summary of Amazonian Resources

1) SEM reviewed near to full reactive Amazonian MK Na-GP matrix; resulting in high 1-day compressive strength of 83.4 MPa and flexural strength of 10.5 MPa 2) XRD confirmed amorphous GP formation with a hump at 28° 2ϴ. 3) Amazonian MK is a viable precursor for geopolymer synthesis Table&1.&&Comparison&of&Mechanical&Properties&of&Portland&Cements&(OPC)&with&(GPC)& & Property& OPC& GPC& Compressive&strength&(MPa)& 60& 100&B&120& Flexure&Strength&(MPa)& 5B6& 10B15& Density&(g/cc)& 2.7& 1.4& Setting&time&(days)& 28& 1& &

Table 2: Flexure Strength of GPCs with Organic or Biological Reinforcements Reinforcement % addition Flexure strength (MPa) Polypropylene chopped fibers (1/2 “) 2.5 wt % 14.5 Polypropylene chopped fibers (1 “) 2.5 wt % 15 Polypropylene chopped fibers (2 “) 2.5 wt % 18.3 Cork particles 60 wt% 2.5 (0.75 % strain to failure) Abaca (banana leaf random fibers) 8.0 wt% 52.3 Corn husk fibers 13 wt % 7.6 (7 % strain to failure) Jute weave 30 wt % 20.5 Colombian fique / sisal (unidirectional) 50 wt % 11.4 Amazonian malva (unidirectional) 5.5 wt % 31.55 Amazonian curaua (unidirectional) 8.3 wt % 18.86 Chopped bamboo in Amazonian kaolinite 15 wt % 6-7

SUMMARY of GP COMPOSITES

• Alkali activated cements are not the same as geopolymers

• A key feature of geopolymers is their formation by dissolution of the aluminosilicate source to - form AlO4 tetrahedra which undergo polycondensation with SiO4 tetrahedra to precipitate out as an inorganic aluminosilicates

• Strong geopolymer composites can be made using ceramic, synthetic or biological reinforcements 42nd International Conference and Expo on Advanced Ceramics and Composites (ICACC’18)

Symposium on Geopolymers (17 conference proceedings to date) January 21 – 26 (2018) Daytona Beach, Fla. USA

Geopolymers II: Versatile Materials Offering High Performance and Low Emissions

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May 27-June 1, 2018 Hotel Dos Templarios Tomar, Portugal